Anthraquinone triazoles



United States Patent ANTHRAQUINONE TRIAZOLES Erwin Klingsberg,Mountainside, N.J., assignor to American Cyanamid Company,"New York,N.Y., a corporation of Maine No Drawing. Application November 18, 1957Serial No. 696,906

6 Claims. cl. 260-308) This invention relates to new triazolederivatives of anthraquinone, and more specifically, it relates to new1,2,4-triazoles, which are substituted in the 3-, 4-, and 5- positions,the 3-position carrying a 2-anthraquinonyl radical and the 4- and5-substituents being aryls. The compounds of my invention can be shownby the following formula:

R1G/ \G-R1 L in which R is a Z-anthraquinonyl radical and R and R arearyls. These compounds are useful as intermediates for vat dyes or asvat dyes themselves.

There are several methods of preparing the compounds of my invention.One such method is described in my copending application Serial No.696,941, filed November 18, 1957. This process involves the reaction ofa carbohydrazide with a chloroimide using the following reaction:

The reaction thus goes through an intermediate amidrazone. In some casesthis spontaneously ring closes to the tn'azole, but in other cases it isnecessary to treat the intermediate amidrazone with agents such asthionyl chloride, phosphorus oxychloride, p-toluenesulfonic acid,sulfuric acid, and the like to efiect the ring closure. This method isespecially useful for preparing the simpler compounds of my inventiondirectly and without complicated hydrazide or in the chloroimide.

l atented Aug. 4, 1959 OCH;

Thus the anthraquinone radical can be in the carbox- Either reactionwith the proper aryl groups in the other positions of the intermediatesgives the same reaction product.

In the above anthraquinonyl tn'azole, the chlorine on the alpha positionon the anthraquinone may be replaced by an amino group by autoclavingwith strong aqueous ammonia or by reaction with p-toluene-sulfonamide inthe presence of a copper catalyst, followed by hydrolysis of the tosylgroup. The resulting amino compound comprises a new vat dye for dyeingcotton red. I

The above method is a quite eiiective and simple direct method ofpreparing the simpler compounds of my invenduced into the triazole ringby this method when the desired substituent in the 1-position appears tointerfere with the condensation of the carboxhydrazide with thechloroimide. Thus, while the l-chloroanthraquinone-Z- carboxhydrazide,e.g., will react in this manner, the 1-aminoanthraquinone-Z-carboxhydrazide will not. Dyes having a l-aminogroup must be prepared by atosylami- .dation, as described above, of thel-chloro anthraquinonyl triazoles. However, in many cases additionalsubstituents in 4-position can only be introduced after the 1-positionof the anthraquinone-Z-carboxylic acid already carried an amino group.Consequently, another and more complicated method for preparing1,2,4-triazoles, which is not my invention, must be resorted to toprepare these more complicated compounds of my invention. In this methodthe desired anthraquinone-Z-carboxylic acid is converted into an arylamide which, upon treatment with a halogen ating agent such as thionylchloride or phosphorus pentachloride, forms the correspondinganthraquinonyl aryl chloroimide. This chloroimide is 'then reacted withhydrazine or hydrazine hydrate in indifferent solvents, as for exampledioxane, to form an anthraquinone-Z-carbonylic arylide hydrazone. Whensuch a compound is then reacted With a diaryl chloroimide, there isreadily formed the 1,2,4-triazole. This preparation can be illustratedby the following equation:

oNH, I1

The above vat dye, a red, thus prepared, can now by 'tosylamidation orby reaction with ammonia under pressure be made into a blue dyestufi byreplacement of the bromine with an amino group, followed by acylation.In this latter method of preparation, the anthraquinone must be in thecarboxylic arylidehydrazone reactant. V

The choice of these methods thus depends on the substituents to be inthe anthraquinone ring. With no,sub 'stituents, or substituents in theother anthraquinone ring from the carboxylic acid group, or with asimple chlorine in the 1-position, the first method can be used, havingthe 'anthraquinone group either in the carbohydrazide part of thereaction mixture or in the chloroimide reactant. The introduction ofmore complicated anthraquinonewith other groups in the same ring as thecarbon group, especially with amino in the 1 position, requires the, useof the more complicated second synthesis, except as amino can beintroduced by replacement of the alpha chlorine.

Keeping in mind the above limitation as to the choice of process to beused, the anthraquinone carboxylic acids which may be used as thestarting material for either preparation include:anthraquinone-Z-carboxylic acid; 1- nitro anthraquinone-Z-carboxylicacid, l-chloro anthraquinone-2-carboxylic acid; l-aminoanthraquinone-Z-carboxylic acid; l-methylaminoanthraqtfinone-Z-carboxylic acid; l-methoxy anthraquinone-Z-carboxylidacid; 1- amino-4-nitro anthraquinone-Z-carboxylic acid; 1,4 -diaminoanthraquinone-Z-carboxylic acid; l-amino-4-benzoylaminoantbraquinone-Z-carboxylic acid; S- nitrd anthraquinone-2-carboxylicacid; S-amino anthIaquinone Z-carboxylic acid; S-benzoylaminoanthraquinone-Z-crboriylic acid; and the like. These can be convertedeither: into the hydrazides or into the carboxarylide hydrazones for usein either preparation. They can be reacted with any (lug;

In addition to these compounds, the chloroimides of various arylamidesof anthraquinone-Z-carboxylic acid can be used in the first processmentioned above in conjunction with the carboxyhydrazides of any simplearyl carboxylic acid, such as benzoic acid, toluic acid, methoxy benzoicacid, dimethoxy benzoic acid, chloro benzoic acid, bromo benzoic acid,nitro benzoic acid, meta-tn'fluoro methyl benzoic acid, p-benzoyl aminobenzoic acid; naphthoic acid, such as l-naphthoic, Z-naphthoic acid,3-oxy- 2-naphthoic acid, thenoic acid, nicotinic acid and isomericpyridine carboxylic acids, and the like.

The new tn'azoles of this invention are useful as intermediates for thepreparation of new triazole vat dyes, or are themselves triazole vatdyes when they have present the proper auxochromic groups to give colorand substantivity. Such auxochromic groups include amino, acylamino,chloro, methoxy, and the like. T riazoles in which the anthraquinoneradical contain a nitro group may be readily reduced by the usualreducing agents for nitro groups to form the amino anthraquinonetriazole vat dyes. The amino groups may, if necessary, be acylated togive vat dyes of improved shade and fastness. Such acylation can be witha benzoyl or a substituted benzoyl group or a thenoyl group. In generalred shades are .obtained when there is an amino group present 'in theleposition of the anthraquinone and bluish shades are obtained whenthere are present amino groups or acylamino groups in the 1- and4-position. Amino or acylamino groups in the other ring of theanthraquinone from that attached to the triazole ring have less effecton the shade and in general, give reds or red-browns. Halogens on theanthraquinone ring can be used in the Ullmann reaction to formanthrimides with another amino anthraquinone, and such anthrimides canbe used per se as vat dyes or they can be carbazolized by reaction withaluminum chloride in manner known to those skilled in dye chemistry.Similarly, anthraquinone radicals having halogen can also be reactedwith ammonia or with toluene sulfonamide to introduce another aminogroup into the anthraquinone radical.

My invention can be illustrated .by the following exam ples in whichparts are by weight unless otherwise specified.

Example 1 A solution of 0.32 part ofl-chloro-N-phenyl-Z-anthraquinonecarboximidyl chloride in 15 parts byvolume of o-dichlorobenzene is warmed to about 140 C., and stirred while.012 part of benzhydrazide is added. The mixture is then heated atreflux until triazole formation is complete. It is then cooled, dilutedwith hexane and the product filtered.

quinonecarboximidyl chloride is used, the corresponding -4-toly1triazole is obtained. T Similarly, the N-anisyl and N-pyridylchlorimides give the corresponding 4-.sub-

stituted triazoles.

Example 2 If an equivalent amount of l-chloro-N-tolyl-Z-anthra- I 6 netis then chilled, diluted vvith a little benzene, filtered and washed. Itis identical with that prepared in Example 4.

Example 3 amounts ofthenoyl hydrazide give the triazole with a 2- thenylradical.

Example 4 The triazole of Example l-may be prepared by another method.N-phenylbenz imidyl chloride ,is prepared from 0.3 part of benzanilideby refluxing with 1 part of thionyl chloride, excess thionyl chloridebeing removed by heating. After the addition of 3 parts by volume ofo-dichlorobenzene and 0.3 part of Z-anthraquinone carbohydrazide, themixture is stirred at 189 C., until the reaction is complete, It is thencoole d and'the triazole collected and dried.

This triazole product gives a brown-red vat from which it isrecovered-unchanged on aeration. It is identical with the triazoleobtained by a dilferent method in Example 2.

Example 5 If in the preceding example, N-biphenylbenzimidylchlorideisprepared from 0.376 part of N-p-biphenylbenzamide byreflux'ing with 1part of thionyl chloride and the .P tr azoles e a ve s u ur is obtaine ruct reacted with ,Z-anthraquin'one carbohydra zide, the

Example 6 anilide (prepared from aniline and the acid chloride) isheated in 400 parts of chlorobenzene with 11.6 parts of P01 I Themixture is heated slowly to 100 C. and held there until a solution isobtained. The mixture is filtered and the filtrate is cooled. Thel-aminoarithraquinone-Z- 'carboxylic acid-phenylimide chloride whichseparates'is isolated by filtration and washed with petroleum ether.

Twelve parts of the dried product is mixed with 250 parts of dry freshlydistilled dioxane and the mixture is =heated to 8090 C. Ten parts'ofhydrazine hydrate is added dropwise. The mixture is stirred hot untilthereaction is complete and then cooled. The product,1-aminoanthraquinone-2-carboxylic acid anilide hydrazone, is filtered,washed with methanol and dried.

Six parts of this product is mixed with 3.2 parts of N- neutraland'dried.

phenylbenzimidyl chloride, 160 parts of o-dichlorobeng zene, and 10parts of pyridine. The mixture is heated to reflux until the reaction iscomplete. It is then cooled and the precipitated red product isfiltered, washed with dichlorobenzene and alcohol, and dried. It dyescotton a red shade.

The same productis obtained by reacting the product of Example 1 withammonia in the presence of cuprous chloride under pressure.

The procedure of Example 6 is followed using an equivalent amount of1aamino-4-nitroanthraquinone-2-carboxylic anilide in place of thel-aminoanthraquinone-Z- anthraquinonyl compound, is isolated byfiltration, washed Five parts of the above product is mixed with partsof nitrobenzene and the mixture is stirred at 130 C., while 5 parts ofbenzoyl chloride is added. The mixture is stirred'at 130 C., until thereaction is substantially complete and is then cooled. The precipitatedblue dyestutt is filtered. washed with nitrobenzene and alcohol anddried.

Greener blue dyes are obtained by usingequivalent amounts ofm-trifluoromethyl benzoyl chloride or thenoyl chloride in the aboveacylation step.

Example 9 O NH:

Example 10 N 0: The'procedure of Example 1 is followed using S-nitro--N-phenyl- 2-anthraquinonyl carboximidyl chloride in place of the1-chloro-N-phenyl-Z-anthraquinonyl carboximidyl chloride.

Example 11 One-tenth part of the production of Example 6 is vatted byheating it in a solution of 1 part of sodium carboxylic anilide. Thereddish product is used as an hydrosulfite and 1 part of caustic soda in100 Parts f intermediate for dyes of Example 8.

" Example 8 0 NH, N

water. The mixture is held at 80 C., while a piece of cotton cloth of-5parts by weight is immersed therein for 30 minutes. The cloth is thenoxidized and soaped. The cloth is dyed a red shade.

Similarly, the product of Example dye cotton a blue shade.

I claim:

1. 1,2,4-triazoles substituted in the 3-, 4- and 5-positions, the 3substituents being a 2-anthraquinonyl radical having in its 1-, 4-andS-positions substituentsselected from the group-consistingfofhydrogen, nine-chloro, amino, benzoylamino, thenohylamino' andm-trifluoro methyl benzoylamino; the said Z-anthraquinonyl, radical8canbeusedto having no more thantwo such substituents, the 4 and 5substituents in said triazole being arpmatic radicals of less than 3rings, the substituents on which are selected from the group consistingof hydrogen, methyl, methoxy, chloro, bromo, trifluoromet yl, nitro,amino, hydroxy and benzoyl amino, there .being no morethan two suchsubstituentson said aromatic radicals.

or a thenoyl group. -In general red shades are obtained when there is anamino group present in the 1-position of the anthraquinone and bluishshades are obtained when there are present amino groups er, acylaminogroups in the 1- and 4-position. Amino or aeylamino groups in the otherring of the anthraquinone from that attached to the triazole ring haveless effect on the'shade' and in general, give r'eds or red-browns.Halogens on the anthraquinone ring can be used in the Ull'man'n reactionto form anthrimides with another amino anthraquinone, and suchanthrimides can be used per se as vat dyes or they can be carbazolizedby reaction with aluminum chloride in manner known to those skilled indye chemistry. Similarly, anthraquinone radicals having halogen can alsobe reacted with ammonia or with toluene sulfonamide to introduce anotheramino group into the anthraquinone radical.

My invention can be illustrated by the following examples in which partsare by weight unless otherwise speci' fied.

Example I A solution of 0.32 part ofl-chloro-N-phenyl-Z-anthraquinonecarboximidyl chloride in parts byvolume of o-dichlorobenzene is warmed to about 140 C., and stirred while.012 part of benzhydrazide is added. The mixture is then heated atreflux until triazole formation is complete. It is then cooled, dilutedwith hexane and the productfiltered.

If an equivalent amount of l-chloro-N-tolyl-Z-anthraquinonecarboximidylchloride is used, the corresponding 4-to1yl triazole is obtained.Similarly, the N-a'nis'yl and N-pyridyl chlorimides-give thecorresponding 4-sub- 'stituted triazoles.

, Example 2 uct is then ehilled, diluted with a little benzene, filteredand washed. It is identical with that prepared in Example 4.

Example 3 In the preceding example, if instead of 1.0 partbenzhydrazide, 1.35.part-s of 2-naphthoic acid hydrazide are used, atriazole corresponding to the above formula is obtained. Similarly, theuse of equivalent amounts of nicotinic acid hydrazide, instead, producesthe compound having a 2- ipyridyl' radical in place of the naphthyl;Equivalent amounts of thenoyl hydrazide give the triazole witha 2-thenyl radical. Y

Example 4 The triazole of Example .2 may be prepared by another method.N-phenylbenzimidyl chloride is prepared from 0.3 part of benzanilide byrefluxing with 1 part of thionyl chloride, excess thionyl chloride beingremoved by heating. After the addition of 3 parts by volume ofo-diehlorobenzene and 03 part of Z-anthraquinone carbohydrazide, themixture is stirred at C., until the reaction is complete. VB isthenucool'ed" and the triazole collected and dried.

This triazole product gives a brown-red vat from which it is recoveredunchanged on aeration. It is identical with the triazole obtained by adiiierent method in Example 2.

Example 5 If in the preceding example, N-biphenylbenzimidylchlorigle isprepared from 0.3 76 part of N-p-biphenylbenzamide by refluxing with 1part of thionylchlorideand the product reacted with Z-anthraquinonecarbohydrazidqthe riazo e f t e a ve s r u is Qb a n e asserts amt-ea:

Twenty parts of l-aminhanthraquinone-Z-carboxylic anilide (prepared fromaniline and the acid chloride) is added dropwise. The mixture is stirredhot until the reaction is complete and then cooled. The product,l-aminoanthraquinone-2-carboxylic acid anilide hydrazone, is filtered,washed with methanol and dried.

Six parts of this product is mixed with 3.2 parts of N- phenylbenzimidylchloride, 160 parts of o-dichlorobenzone, and 10 parts of pyridine. Themixture is heated to reflux until thereaction is complete. It is thencooled and the precipitated red product is filtered, washed withdichlorobenzene and alcohol and dried. It dyes cotton a red shade.

The same productis obtained by reacting the product of Example 1 withammonia in the presence of cuprous chloride under pressure.

Example 7 O NH:

| /N\ V v A NO: V i l V i The procedure of Example 6 is followed usingan equivalent amount of 1-amino-4-nitroanthraquinone-2-carboxylicanilide in place of the l-aminoanthraquinone-Z- carboxylic anilide. Thereddish product is used as an intermediate for dyes of Example 8.

" Ten parts of thejprod lctfof Example is added? gradually to arefluxing solution oiSQ parts or sodium sulfide in'450 parts ofwater.The mixture is refl uxed forseveral hours and cooled. "rnepmdua, the1,4-diaminoanthraouinonyl compound, is isolated by filtration, washedneutral and dried.

1 Five parts'of the above product is mixed with50 parts of nitrobenzeneand the mixture is stirred at 130 C., while 5 parts of benzoyl chlorideis added. The mixture is stirred at 130 C., until the reaction issubstantially complete and is then cooled. The precipitated bluedyestuii is filtered, washed with nitrobenzene and alcohol andpdriedr I.Greener blue dyes are obtained by using equivalent amounts ofm-trifluoromethyl benzoyl chloride or thenoyl chloride in the aboveacylation step.

' Example 9 I The procedure of Example 6 is used with equivalent amountsof N-p-tolyl-Z-naphthimidyl chloride replacing the N-phenylbenzimidylchloride." Similarly, other aryl groups are placed into the 4-andS-position in the triazole structure by using insteadN-phenyl-Z-thiophenecarboximidyl chloride, N-phenylnicotinimidylchloride, or Npanisyl-2,4 dichlorobenzimidyl chloride.

-Example 10 Nmii The procedure of Example 1 isfollowed using S-nitro-N-phenyl-2-anthraquinonyl carboximidyl chloride in place of the1-chloro-N-phenyl-Z-anthraquinonyl carboximidyl chloride.

Example. 11

One-tenth part of the production of Example 6 is vatted by heating it ina solution of 1 part of sodium hydrosulfite and 1 part of caustic sodain parts of water. The mixture is held at 70;-80 C., while a piece ofcotton cloth of-S parts by weight is immersed therein for 30 minutes.The cloth is then oxidized and soaped. The cloth is dyed a red shade.

Similarly, the product of Example 8 can be used to dye cotton a blueshade.

I claim: a.

1. 1,2,4triazo1es substituted in the 3-, 4- and 5-positions, the 3substituents being a Z-anthraquinonyl radical having. in its 1-, 4- and5spositions substituents selected from the groupconsistingof hydrogen,nitro,.chloro, amino, benzoylamino, thenonylamino and m-tn'fluoro methylbenzoylamino; the said Z-anthraquinonyl radical having no more than twosuchsubstituentsthe 4 and 5 substituents'injsaid triazole being aromaticradicals of less than 3 rings, the substituents on which are selectedfrom the group consisting of hydrogen, methyl, methoxy, chloro, bromo'trifluoromethyl, nitro, amino, hydroxy and benzoyl amino, there beingno morethan twosuch substituents on said aromatic radicals.

2. The compound:

3. The compound:

4. The compound:

5. The compound:

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noo2,898,343 August 4, 1959 Erwin Klingeberg It s herebjr certified thaterror appears in the-printed specification 1 of the above numberedpatent requiring correction and that the said Letters Patent should readas corrected below.

Column 3, line 43, for "anthraq uinone" read antliraquinones line 44,for carbon read carbonyl column 8, line 67, for "thenonylamino" read anthenoylamino Signed and sealed this 9th day of February 1960 SEAL)Attest:

KARL H, AEGLINE ROBERT C. WATSON Attesting Officer Commissioner ofPatents

1. 1, 2,4-TRIAZOLES SUBSTITUTED IN THE 3-, 4- AND 5-POSITIONS, THE 3SUBSTITUENTS BEING A 2-ANTHRAQUINONYL RADICAL HAVING IN ITS 1-, 4- AND5-POSITIONS SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN,NITRO, CHLORO, AMINO, BENZOYLAMINO; THENONYLAMIO AND M-TRIFLUORO METHYLBENZOYLAMINO; THE SAID 2-ANTHRAQUINONYL RADICAL HAVING NO MORE THAN TWOSUCH SUBSTITUENTS, THE 4 AND 5 SUBSTITUENTS IN SAID TRIAZOLE BEINGAROMATIC RADICALS OF LESS THAN 3 RINGS, THE SUBSTITUENTS ON WHICH ARESELECTED FROM THE GROUP CONSISTING OF HYDROGEN, METHYL, METHOXY, CHLORO,BROMO, TRIFLUOROMETHYL, NITRO, AMINO, HYDROXY AND BENZOYL AMINO, THEREBEING NO MORE THAN TWO SUCH SUBSTITUENTS ON SAID AROMATIC RADICALS.